WO2009099567A2 - Polysaccharides réticulés et procédés de production - Google Patents

Polysaccharides réticulés et procédés de production Download PDF

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Publication number
WO2009099567A2
WO2009099567A2 PCT/US2009/000617 US2009000617W WO2009099567A2 WO 2009099567 A2 WO2009099567 A2 WO 2009099567A2 US 2009000617 W US2009000617 W US 2009000617W WO 2009099567 A2 WO2009099567 A2 WO 2009099567A2
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WIPO (PCT)
Prior art keywords
particles
polysaccharide
derivatized
titanium
guar
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PCT/US2009/000617
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English (en)
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WO2009099567A3 (fr
Inventor
Caroline Mabille
Kraig Luczak
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Rhodia Inc.
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Publication date
Application filed by Rhodia Inc. filed Critical Rhodia Inc.
Priority to CA2713849A priority Critical patent/CA2713849C/fr
Priority to CN2009801038361A priority patent/CN101932610B/zh
Priority to BRPI0907029-0A priority patent/BRPI0907029A2/pt
Priority to EP09708519.5A priority patent/EP2245073A4/fr
Publication of WO2009099567A2 publication Critical patent/WO2009099567A2/fr
Publication of WO2009099567A3 publication Critical patent/WO2009099567A3/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H1/00—Processes for the preparation of sugar derivatives
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K31/00—Medicinal preparations containing organic active ingredients
    • A61K31/70—Carbohydrates; Sugars; Derivatives thereof
    • A61K31/715—Polysaccharides, i.e. having more than five saccharide radicals attached to each other by glycosidic linkages; Derivatives thereof, e.g. ethers, esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof

Definitions

  • the present invention relates to crosslinked polysaccharides and methods of preparation thereof and, in particular, glyoxal and glyoxal/titanium crosslinked guar and methods of preparation thereof.
  • Guars are commercially available in several forms, including derivatized and underivatized.
  • the derivatized forms are cationic, non-ionic, and anionic, and combinations of cationic, non-ionic, and anionic.
  • the derivatized guar splits and gums are carboxyl methyl guar gums, hydroxypropyl guar gums, and hydroxypropyl trimethylammonium guar gums, which are commercially available materials used in a variety of applications and are typically made by a "water-splits" process, wherein material, known as guar "splits", derived from guar seeds undergoes reaction with a derivatizing agent in an aqueous medium.
  • guars have been used extensively in many fields.
  • personal care, household care, and pet care formulations including but not limited to: shampoos, body washes, hand soaps, lotions, creams, conditioners, shaving products, facial washes, neutralizing shampoos, personal wipes, other hair care products and skin treatments.
  • Guars are conventionally produced by milling at an alkaline pH and then crosslinked with Borax (sodium tetra borate).
  • Borax is commonly used as a processing aid in the reaction step of the water-splits process to partially crosslink the surface of the guar splits and thereby reduces the amount of water absorbed by the guar splits during washing.
  • the borate crosslinking takes place under alkaline conditions and is reversible, allowing the product to hydrate under acidic conditions.
  • TMA trimethylamine
  • the present invention is directed to a method for making crosslinked derivatized polysaccharides, comprising the steps of: (a) contacting particles of a polysaccharide with a titanium compound in an aqueous medium having an alkaline pH under conditions appropriate to intra-particulately crosslink the particles; (b) reacting, prior to or after the step of contacting the particles of polysaccharide with the titanium compound, the particles of polysaccharide with a derivatizing agent under conditions appropriate to produce derivatized polysaccharide particles; (c) washing the titanium crosslinked and derivatized particles; (d) contacting, concurrently with or after the step of washing the titanium crosslinked and derivatized particles, such particles with an aqueous medium having an acidic pH under conditions appropriate to substantially de-crosslink the particles; and (e) contacting, concurrently with or after step (d), the de- crosslinked particles with a glyoxal compound under conditions appropriate to intra-particulately crosslink
  • present invention is directed to a method for making crosslinked derivatized polysaccharides, comprising the steps of: (a) contacting particles of a polysaccharide with a titanium compound in an aqueous medium having a pH greater than about 10 under conditions appropriate to intra-particulately crosslink the particles; (b) reacting, prior to or after the step of contacting the particles of polysaccharide with the titanium compound, the particles of polysaccharide with a derivatizing agent under conditions appropriate to produce derivatized polysaccharide particles; (c) washing the titanium crosslinked and derivatized particles; (d) contacting such particles with an aqueous medium having an acidic pH under conditions appropriate to substantially de-crosslink the particles; and (e) contacting, concurrently with or after step (d), the de-crosslinked particles with a glyoxal compound under conditions appropriate to intra- particulately crosslink the particles.
  • the present invention is directed to a method for making crosslinked derivatized polysaccharides, comprising the steps of: (a) contacting particles of a polysaccharide with a titanium compound in an aqueous medium having pH greater than about 10 under conditions appropriate to intra-particulately crosslink the particles; (b) reacting, prior to or after the step of contacting the particles of polysaccharide with the titanium compound, the particles of polysaccharide with a derivatizing agent under conditions appropriate to produce derivatized polysaccharide particles; (c) washing the titanium crosslinked and derivatized particles; (d) contacting the titanium crosslinked and derivatized particles with an aqueous medium having a pH less than about 10 under conditions appropriate to substantially de-crosslink the particles; and (e) contacting the de-crosslinked particles with a glyoxal compound in an aqueous medium having a pH less than about 7 under conditions appropriate to intra-particulately crosslink the particles.
  • the aforementioned steps of contacting the titanium crosslinked and derivatized particles with an aqueous medium in step (d), contacting the de-crosslinked particles with a glyoxal compound in step (e) or both is performed through spraying.
  • the present invention is directed to a method for producing a crosslinked polysaccharide comprising: (a) reacting particles of polysaccharide with a derivatizing agent under conditions appropriate to produce derivatized polysaccharide particles; (b) washing the derivatized polysaccharide particles; and (c) contacting, prior to or after the step of washing the derivatized polysaccharide particles, the particles with a glyoxal compound in an aqueous medium under condition appropriate to crosslink the derivatized polysaccharide particles.
  • the present invention is a personal care product comprising the polysaccharides made by any of the methods described above.
  • the guar made according to the method of the present invention has no intentionally added boron, but may comprise small amounts of boron impurities, for example, as a naturally occurring component of guar splits or process fluids used in the method.
  • the boron content of the material is less than about 50 parts per million (ppm") boron, that is, less than about 50 parts by weight boron per one million parts by weight of the material, more typically less than about 20 ppm, and even more typically less than 5 ppm.
  • aqueous medium generally means a liquid medium that contains water, typically greater than or equal to 10 wt% water, more typically greater than or equal to 25 wt% water, even more typically greater than or equal to 50 wt% water and less than 90 wt%, more typically less than 75 wt%, and even more typically less than 50 wt% of one or more water miscible organic liquids, such as for example, an alcohol, such as ethanol or iso-propanol, and may, optionally contain one or more solutes dissolved in the aqueous medium.
  • the liquid portion of an aqueous medium consists essentially of water.
  • aqueous solution refers more specifically to an aqueous medium that further comprises one or more solutes dissolved in the aqueous medium.
  • intra-particulately means within each discrete particle of the polysaccharide and intra-particulate crosslinking thus refers to crosslinking between polysaccharide molecules of a discrete polysaccharide particle, typically between hydroxyl groups of such polysaccharide molecules, with no significant crosslinking between particles.
  • Suitable polysaccharides contain polymeric chains of saccharide constitutive units, and include, for example, starches, celluloses, xanthans, such as xanthan gum, polyfructoses such as levan, and galactomannans such as guar gum, locust bean gum, and tara gum.
  • the polysaccharides are not completely soluble in the aqueous medium and thus typically remain as a discrete solid phase dispersed in the aqueous medium.
  • the polysaccharide is a locust bean gum. Locust bean gum or carob bean gum is the refined endosperm of the seed of the carob tree, Ceratonia siliqua. The ratio of galactose to mannose for this type of gum is about 1 :4. In one embodiment, the polysaccharide is a tara gum. Tara gum is derived from the refined seed gum of the tara tree. The ratio of galactose to mannose is about 1 :3.
  • the polysaccharide is a polyfructose.
  • Levan is a polyfructose comprising 5-membered rings linked through ⁇ -2,6 bonds, with branching through ⁇ -2,1 bonds.
  • Levan exhibits a glass transition temperature of 138°C and is available in particulate form. At a molecular weight of 1-2 million, the diameter of the densely-packed spherulitic particles is about 85 nm.
  • the polysaccharide is a xanthan.
  • Xanthans of interest are xanthan gum and xanthan gel.
  • Xanthan gum is a polysaccharide gum produced by Xathomonas campestris and contains D- glucose, D-mannose, D-glucuronic acid as the main hexose units, also contains pyruvate acid, and is partially acetylated.
  • the polysaccharide of the present invention is derivatized or non-derivatized guar.
  • Guar comes from guar gum, the mucilage found in the seed of the leguminous plant Cyamopsis tetragonolobus.
  • the water soluble fraction (85%) is called "guaran,” which consists of linear chains of (1 ,4)-. ⁇ -D mannopyranosyl units-with ⁇ -D- galactopyranosyl units attached by (1 ,6) linkages.
  • the ratio of D-galactose to D-mannose in guaran is about 1 :2.
  • Guar gum typically has a weight average molecular weight of between 2,000,000 and 5,000,000 Daltons.
  • the guar seeds used to make guar gum are composed of a pair of tough, non-brittle endosperm sections, hereafter referred to as "guar splits," between which is sandwiched the brittle embryo (germ). After dehulling, the seeds are split, the germ (43-47% of the seed) is removed by screening.
  • the splits typically contain about 78-82% galactomannan polysaccharide and minor amounts of some proteinaceous material, inorganic salts, water-insoluble gum, and cell membranes, as well as some residual seedcoat and seed embryo.
  • Processes for making derivatives of polysaccharides are generally known.
  • the polysaccharide is reacted with one or more derivatizing agents under appropriate reaction conditions to produce a guar polysaccharide having the desired substituent groups.
  • Suitable derivatizing reagents are commercially available and typically contain a reactive functional group, such as an epoxy group, a chlorohydrin group, or an ethylenically unsaturated group, and at least one other substituent group, such as a cationic, nonionic or anionic substituent group, or a precursor of such a substituent group per molecule, wherein substituent group may be linked to the reactive functional group of the derivatizing agent by bivalent linking group, such as an alkylene or oxyalkylene group.
  • Suitable cationic substituent groups include primary, secondary, or tertiary amino groups or quaternary ammonium, sulfonium, or phosphinium groups.
  • Suitable nonionic substituent groups include hydroxyalkyl groups, such as hydroxypropyl groups.
  • Suitable anionic groups include carboxyalkyl groups, such as carboxymethyl groups. The cationic, nonionic and/ or anionic substituent groups may be introduced to the guar polysaccharide chains via a series of reactions or by simultaneous reactions with the respective appropriate derivatizing agents.
  • the derivatized guar of the present invention includes but is not limited to hydroxypropylguar (HPG), carboxymethylguar (CMG), hydroxyethyl guar (HEG), carboxymethylhydroxypropyl guar (CMHPG), hydroxybutyl guar (HBG), cationic guar, hydrophobically modified guar (HMG), hydrophobically modified carboxymethylguar (HMCMG), hydrophobically modified hydroxyethylguar (HMHEG), hydrophobically modified hydroxypropylguar (HMHPG), hydrophobically modified carboxymethylhydroxypropylguar (HMCMHPG), hydrophobically modified hydroxybutyl guar (HMHBG), and hydrophobically modified cationic guar (HMCG).
  • HPG hydroxypropylguar
  • CMG carboxymethylguar
  • HEG hydroxyethyl guar
  • CMHPG carboxymethylhydroxypropyl guar
  • HMHPG
  • the polysaccharide is reacted with an alkylene oxide derivatizing agent, such as ethylene oxide, propylene oxide, or butylene oxide, under known alkoxylation conditions to add hydroxyalkyl and/or poly(alkyleneoxy) substituent groups to the guar polysaccharide chains.
  • an alkylene oxide derivatizing agent such as ethylene oxide, propylene oxide, or butylene oxide
  • the polysaccharide is reacted with a carboxylic acid derivatizing agent, such as sodium monochloroacetate, under known esterification conditions to add carboxyalkyl groups to the guar polysaccharide chains.
  • a carboxylic acid derivatizing agent such as sodium monochloroacetate
  • the derivatizing agent can comprise a cationic substituent group that comprises a cationic nitrogen radical, more typically, a quaternary ammonium radical, for example.
  • Typical quaternary ammonium radicals are trialkylammonium radicals, such as trimethylammonium radicals, triethylammonium radicals, tributylammonium radicals, aryldialkylammonium radicals, such as benzyldimethylammonium radicals, radicals, and ammonium radicals in which the nitrogen atom is a member of a ring structure, such as pyridinium radicals and imidazoline radicals, each in combination with a counterion, typically a chloride, bromide, or iodide counterion.
  • the cationic substituent group is linked to the reactive functional group of the cationizing agent, for example, by an alkylene or oxyalkylene linking group.
  • Suitable cationizing reagents include, for example, epoxy- functional cationic nitrogen compounds, such as, for example, 2,3- epoxypropyltrimethylammonium chloride; chlorohydrin-functional cationic nitrogen compounds, such as, for example, 3-chloro-2-hydroxypropyl trimethylammonium chloride, 3-chloro-2-hydroxypropyl- lauryldimethylammonium chloride, 3-chloro-2-hydroxypropyl- stearyldimethylammonium chloride; and vinyl-, or (meth)acrylamide- functional nitrogen compounds, such as methacrylamidopropyl trimethylammonium chloride.
  • epoxy- functional cationic nitrogen compounds such as, for example, 2,3- epoxypropyltrimethylammonium chloride
  • chlorohydrin-functional cationic nitrogen compounds such as, for example, 3-chloro-2-hydroxypropyl trimethylammonium chloride, 3-chloro-2-hydroxypropyl- lauryldimethylammonium chloride, 3-
  • the guar splits are reacted with a chlorohydrin-functional quaternary ammonium compound in the presence of base, in an aqueous medium under relatively mild conditions, such as heating to a temperature of about 20 0 C to about 85 0 C, typically about 40 0 C to about 70 0 C, to produce cationic guar splits, that is, derivatized guar splits having cationic functional groups.
  • the derivatized guar splits can comprise molecules of guar having one or more substituent groups per molecule of guar, wherein a first portion of the substituent groups is added by reaction of guar splits with one or more first derivatizing agents under appropriate reaction conditions in a first liquid medium, and a second portion of the substituent groups have been added by reaction of the guar splits with one or more second derivatizing agents in a second liquid medium under appropriate reaction conditions, wherein at least one of the first liquid medium and the second liquid medium is an aqueous medium.
  • the derivatized guar splits produced by reaction of guar splits with a derivatizing agent in an aqueous medium can be in the form of water- swollen gum comprising (i) from about 30 to 60 parts by weight (“pbw"), more typically from 30 to 50 pbw of cationic guar splits per 100 pbw of water-swollen gum and (ii) from about 40 to 70 pbw, more typically 50 to 70 pbw of water per 100 pbw of water-swollen gum.
  • the step of contacting the derivatized guar splits with an aqueous wash medium can be conducted prior to, concurrent with or after the step of the reaction of guar splits with a derivatizing agent in an aqueous reaction medium under appropriate reaction conditions.
  • the water-swollen gum produced by reaction of guar splits with a derivatizing agent in an aqueous reaction medium is contacted with the aqueous wash medium.
  • the derivatized guar splits can then be allowed to cool, typically to a temperature of less than or equal to about 50 0 C prior to washing the derivatized guar splits.
  • the derivatized guar splits can then be washed with the aqueous medium by contacting the derivatized guar splits with the aqueous medium and then physically separating the aqueous wash medium, in the form of an aqueous rinse solution, from the derivatized guar splits, wherein the contacting and separating steps taken together constitute one "wash step" or "washing" step.
  • an aqueous wash medium comprising from about 0.1 to about 30 pbw of a glyoxal can be used.
  • Each wash step is conducted as a batch process, such as for example, in a stirred mixing vessel, or as a continuous process, such as for example, in a column wherein a stream of the derivatized guar splits is contacted with a co-current or counter-current stream of aqueous wash medium.
  • the aqueous wash medium can comprise water and, optionally, up to 25 pbw water miscible organic liquid per 100 pbw of aqueous medium.
  • Suitable water miscible organic liquids include, for example, alcohols such as methanol or ethanol. More typically, the aqueous wash medium consists essentially of water, even more typically, of deionized water.
  • the derivatized guar splits can be contacted with, for example, from about 2 to about 30 kilograms ("kg"), more typically from about 5 to about 20 kg, even more typically from about 5 to about 15 kg, of aqueous wash medium per kg of derivatized guar splits solids per wash step.
  • a method for producing crosslinked guar particles comprises
  • the crosslinking step can be conducted by contacting the derivatized guar splits with glyoxal-containing aqueous wash medium, to at least partially crosslink the hydroxyl groups of the respective guar particles, for a contact time of up to about 30 minutes, more typically from about 30 seconds to about 15 minutes, even more typically from about 1 minute to about 8 minutes, per high salt wash step.
  • the crosslinking step involves contacting the derivatized guar splits with a glyoxal compound after an aqueous wash step.
  • the glyoxal compound is typically in an aqueous solution comprising from about 0.1 to about 30 pbw of glyoxal per 100 pbw of the total mixture.
  • the mixture may also contain an effective amount of an acid to lower the pH below 7.
  • Contacting the derivatized guar splits with a glyoxal compound at least partially crosslinks the hydroxyl groups of the respective guar particles.
  • Crosslinking typically takes place intra-particulately, that is, within each discrete particle of guar splits, between the hydroxyl groups of the particle, without any significant crosslinking between guar splits particles.
  • Contacting the derivatized guar splits with glyoxal compound may comprise various methods including but not limited to a spraying process.
  • titanium compounds are contacted with the derivatized or underivatized guar particles prior to or concurrently with the first wash step.
  • Contacting the guar particles with titanium compounds in such a manner at least partially crosslinks the hydroxyl groups of the respective guar particles, thus making the guar particles less susceptible to loss during the wash step, i.e, when physically separating the aqueous wash medium, in the form of an aqueous rinse solution, from the derivatized guar splits. This, in turn, likely increases total derivatized guar yield.
  • an aqueous dispersion of the titanium crosslinked guar is maintained at a pH of greater than or equal to about 8, more typically greater than or equal to about 10, more typically greater than or equal to about 12, to maintain the guar in the form of substantially water insoluble crosslinked particles to maintain the fluidity of the aqueous dispersion.
  • Crosslinking of the titanium crosslinked guar is reversible and the kinetics of de-crosslinking are pH sensitive.
  • the titanium crosslinked guar particles are de-crosslinked in a solution having a pH of less than about 8. The rate at which de-crosslinking of the guar particles occurs typically increases with decreasing pH.
  • the de-crosslinking rate can be increased by adjusting the pH of the aqueous medium to a value of less than or equal to about 8, more typically less than or equal to about 7 and allows dissolution of the de-crosslinked guar in the aqueous medium, typically to form a viscous aqueous solution of the guar in the aqueous medium.
  • the de-crosslinked guar can then be again crosslinked with a glyoxal compound to maintain the guar particles in the form of an acid dispersion of substantially water insoluble crosslinked particles (thus maintaining the fluidity of the aqueous dispersion). It is desirable in certain formulations to utilize crosslinked guar particles in an acid dispersion.
  • a method for producing crosslinked guar particles comprises: (a) contacting guar particles with a titanium compound in an aqueous medium having an alkaline pH under conditions appropriate to intra-particulately crosslink the particles; (b) reacting, prior to or after the step of contacting the guar particles with the titanium compound, the guar particles with a derivatizing agent under conditions appropriate to produce derivatized guar particles; (c) washing the titanium crosslinked and derivatized particles; (d) contacting, concurrently with or after the step of washing the titanium crosslinked and derivatized particles, such particles with an aqueous medium having an acidic pH under conditions appropriate to substantially de-crosslink the particles; and (e) contacting, concurrently with or after step (d), the de- crosslinked particles with a glyoxal compound under conditions appropriate to intra-particulately crosslink the particles.
  • Suitable titanium compounds are those titanium (II), Titanium (III), titanium (IV), and titanium (Vl) compounds that are soluble in the aqueous medium.
  • the titanium compound is a titanium (IV) compound, that is, a titanium compound in which the titanium atoms of the compound are in the +4 oxidation state.
  • the titanium compound comprises one or more titanium chelates.
  • Suitable titanium chelates are commercially available and include but are not limited to titanium acetylacetonates, triethanolamine titanates, and titanium lactates
  • the titanium compound comprises one or more titanium esters.
  • Suitable titanium esters are commercially available and include but are not limited to n-butyl polytitanates, titanium tetrapropanolate, octyleneglycol titanates, tetra-n-butyl titanates, tetra-n- buytl titanates, tetra-2-ethylhexyl titanates, tetra-isopropyl titanate, and tetra-isopropyl titanate.
  • the titanium compound is selected from diisopropyl di-triethanolamino titanate, titanate (2-), dihydroxy bis [2- hydroypropanato (2-)-O1 , O2], ammonium salt, titanium acetylacetonate, titanium ortho ester, titanium (IV) chloride, and mixtures thereof.
  • the guar particles are contacted with the titanium compound in the aqueous medium under conditions appropriate to at least partially intra-particulately crosslink the hydroxyl groups of the respective guar particles.
  • aqueous medium comprises, based on 100 pbw of the medium, from about 0.1 to about 15 pbw, more typically from about 0.5 to about 10 pbw, and even more typically from about 1 to about 5 pbw, of the titanium compound.
  • guar particles are contacted with titanium compound in the aqueous medium at a temperature of from about 10 to about 90 0 C 1 more typically from about 15 to about 35 0 C, and even more typically, from about 20 to about 30 0 C.
  • the guar particles are contacted with titanium compound in the aqueous medium for a time period of from about 1 minute to about 2 hours, more typically from about 5 minutes to about 60 minutes, and even more typically from about 15 to about 35 minutes.
  • a method for producing crosslinked guar particles comprises: (a) contacting guar particles with a glyoxal compound in an aqueous medium under conditions appropriate to intra-particulately crosslink the particles; (b) reacting, prior to or after the step of contacting the guar particles with the glyoxal compound, the guar particles with a dehvatizing agent under conditions appropriate to produce derivatized guar particles; (c) washing the glyoxal crosslinked and derivatized particles; (d) contacting, concurrently with or after the step of washing the glyoxal crosslinked and derivatized particles, such particles with an aqueous medium having an pH appropriate to substantially de-crosslink the particles; and (e) contacting, concurrently with or after step (d), the de-crosslinked particles with a titanium compound under conditions appropriate to intra-particulately crosslink the particles.
  • the washed derivatized splits can be separated from the aqueous wash medium by any suitable dewatering means such as for example, filtration and/or centrifugation. In one embodiment, the washed derivatized splits are separated from the wash liquid by centrifugation. [0060]
  • the dewatered derivatized splits can have a water content of less than or equal to about 90 wt.%, more typically less than or equal to about 85 wt. % and even more typically less than or equal to about 80 wt. %.
  • the dewatered guar splits are dried and ground to produce derivatized guar particles.
  • the guar can be dried by any suitable drying means, such as, for example, air drying, fluid bed drying, flash grinding, freeze drying, to a moisture content of less than or equal to about 20 wt%, more typically less than or equal to about 15 wt%.
  • suitable drying means such as, for example, air drying, fluid bed drying, flash grinding, freeze drying, to a moisture content of less than or equal to about 20 wt%, more typically less than or equal to about 15 wt%.
  • the dried guar splits can be ground by any suitable particle size reduction means, such as, for example, a grinding mill.
  • the guar splits are simultaneously dried and ground in a "flash milling" procedure, wherein a stream of guar splits and a stream of heated air are simultaneously introduced into a grinding mill.
  • the guar according to the present invention is especially useful in personal, household, and pet care applications, such as, for example, shampoos, body washes, hand soaps, lotions, creams, conditioners, shaving products, facial washes, neutralizing shampoos, personal wipes, and skin treatments.
  • the personal care compositions comprise cationic guar of the invention and one or more "benefit agents" that is, materials known in the art that provide a personal care benefit, such as moisturizing or conditioning, to the user of the personal care composition, such as, for example, cleansing agents such as anionic surfactants, cationic surfactants, amphoteric surfactants, zwittehonic surfactants and non-ionic surfactants, as well as emollients, moisturizers, conditioners, polymers, vitamins, abrasives, UV absorbers, antimicrobial agents, anti-dandruff agents, fragrances, depigmentation agents, reflectants, thickening agents, detangling/wet combing agents, film forming polymers, humectants, amino acid agents, antimicrobial agents, allergy inhibitors, anti-acne agents, anti- aging agents, anti-wrinkling agents, antiseptics, analgesics, antitussives, antipruritics, local an
  • the cationic guars of the invention aid in the delivery of the benefit agent onto and/or into the skin, hair, and/or nails.
  • the personal care composition according to the present invention can be an aqueous composition that comprises, based on 100 pbw of the composition:
  • a surfactant selected from cationic surfactants, anionic surfactants, amphoteric surfactants, zwitterionic surfactants, nonionic surfactants, and mixtures thereof.
  • the surfactant component (b) the personal care composition according to the present invention can comprise a zwitterionic surfactant, more typically a zwitterionic surfactant selected from alkyl betaines and amidoalkylbetaines.
  • the surfactant component (b) the personal care composition according to the present invention can comprise a mixture of a zwitterionic surfactant, more typically a zwitterionic surfactant selected from alkyl betaines and amidoalkylbetaines, and an anionic surfactant, more typically selected from salts of alkyl sulfates and alkyl ether sulfates.
  • Anionic surfactants suitable for use in the personal care compositions are well known in the art, and include, for example, ammonium lauryl sulfate, ammonium laureth sulfate, triethylamine lauryl sulfate, triethylamine laureth sulfate, triethanolamine lauryl sulfate, triethanolamine laureth sulfate, monoethanolamine lauryl sulfate, monoethanolamine laureth sulfate, diethanolamine lauryl sulfate, diethanolamine laureth sulfate, lauric monoglyceride sodium sulfate, sodium lauryl sulfate, sodium laureth sulfate, potassium lauryl sulfate, potassium laureth sulfate, sodium lauryl sarcosinate, sodium lauroyl sarcosinate, lauryl sarcosine, cocoyl sarcosine
  • Zwitterionic surfactants suitable for use in the personal care compositions are well known in the art, and include, for example, those surfactants broadly described as derivatives of aliphatic quaternary ammonium, phosphonium, and sulfonium compounds, in which the aliphatic radicals can be straight or branched chain, and wherein one of the aliphatic substituents contains from about 8 to about 18 carbon atoms and one contains an anionic group such as carboxy, sulfonate, sulfate, phosphate or phosphonate.
  • Nonionic surfactants suitable for use in the personal care compositions are well known in the art, and include, for example, long chain alkyl glucosides having alkyl groups containing about 8 carbon atoms to about 22 carbon atoms, coconut fatty acid monoethanolamides such as cocamide MEA, coconut fatty acid diethanolamides, and mixtures thereof.
  • compositions according to the present invention may, optionally, further comprise other ingredients, in addition to benefit agents, such as, for example, preservatives such as benzyl alcohol, methyl paraben, propyl paraben, and imidazolidinyl urea, electrolytes, such as sodium chloride, sodium sulfate, and sodium citrate, thickeners, such as polyvinyl alcohol, pH adjusting agents such as citric acid and sodium hydroxide, pearlescent or opacifying agents, dyes, and sequestering agents, such as disodium ethylenediamine tetra-acetate.
  • benefit agents such as, for example, preservatives such as benzyl alcohol, methyl paraben, propyl paraben, and imidazolidinyl urea
  • electrolytes such as sodium chloride, sodium sulfate, and sodium citrate
  • thickeners such as polyvinyl alcohol
  • pH adjusting agents such as citric acid and sodium hydroxide
  • the boron-free guar of the invention is prepared by comprising reacting the guar with glyoxal at a pH of less than about 6, wherein no boron crosslinker is introduced. In certain embodiments about 0.01 to about 30 parts by weight glyoxal per 100 parts by weight guar is used. In certain embodiments Bronsted acid is reacted with alkaline guar to adjust pH to less than about 6 either prior to, simultaneously with, or after introducing the glyoxal to the guar.
  • preferred fatty esters include, but are not limited to, isopropyl isostearate, hexyl laurate, isohexyl laurate, isohexyl palmitate, isopropyl palmitate, decyl oleate, isodecyl oleate, hexadecyl stearate, decyl stearate, isopropyl isostearate, dihexyldecyl adipate, lauryl lactate, myristyl lactate, cetyl lactate, oleyl stearate, oleyl oleate, oleyl myristate, lauryl acetate, cetyl propionate, and oleyl adipate.
  • fatty esters suitable for use in the personal care compositions are those known as polyhydric alcohol esters.
  • polyhydric alcohol esters include alkylene glycol esters.
  • Still other fatty esters suitable for use in the personal care compositions are glycerides, including, but not limited to, mono-, di-, and tri-glycerides, preferably di- and tri-glycerides, more preferably triglycerides.
  • glycerides including, but not limited to, mono-, di-, and tri-glycerides, preferably di- and tri-glycerides, more preferably triglycerides.
  • a variety of these types of materials can be obtained from vegetable and animal fats and oils, such as castor oil, safflower oil, cottonseed oil, corn oil, olive oil, cod liver oil, almond oil, avocado oil, palm oil, sesame oil, lanolin and soybean oil.
  • Synthetic oils include, but are not limited to, triolein and tristearin glyceryl
  • the personal care compositions may also comprise an anti- dandruff active.
  • anti-dandruff actives include pyridinethione salts, azoles, selenium sulfide, particulate sulfur, keratolytic agents, and mixtures thereof.
  • anti-dandruff actives should be physically and chemically compatible with the essential components of the composition, and should not otherwise unduly impair product stability, aesthetics or performance.
  • Active ingredients can be any of the ones mentioned earlier, especially a silicone compound, an organic oil, an anti-dandruff active, a perfume, or combinations thereof.
  • One the several advantages of the invention is the dispersibility of the guar, and in some embodiments another advantage is the higher rate of deposition than that of the corresponding boron crosslinked guar.
  • Conditioners and shampoo compositions which include silicone oil and cationic guar made according to the above described method are very advantageous in that they have improved dispersion, deposition of silicone, are non-yellowing, and do not suffer from TMA odor.
  • Citric Acid (50%) 64.0 67.0 67.0
  • the surfactants blend is prepared by charging the ingredients in a mixing vessel in the following sequence: 36.7 wt. % deionized water, 6.9 wt. % Mirataine BETC30 (30.74% active), 56.3 wt. % Empicol ESB-3M (26.5% active), 0.05 wt. % Kathon CG brand isothiazolone biocide. The blend is mixed until homogeneous.
  • a shampoo is prepared by mixing the ingredients which are charged in the main mixing vessel in the following sequence: 93.9 parts by weight surfactants blend, 1.5 parts by weight dimethicone emulsion (65% active droplet size, approx 0.6 ⁇ m) Mirasil DM 500 000 emulsion, 3 parts by weight guar premix and 1.6 parts by weight NaCI. Between each addition, the shampoo is mixed until homogeneous. After salt addition, pH is checked and adjusted to pH 6.0 - 6.5 if needed using citric acid or NaOH solutions.
  • the method contains 4 steps: A. the pre-treatment of the hair tresses with a 10% SLES (sodium lauryl ether sulfate) solution, B. the treatment of the hair tresses with the shampoo, C. the dimethicone extraction using THF (Tetrahydrofuran) and D. the dosage of the extracted dimethicone using GPC.
  • SLES sodium lauryl ether sulfate
  • THF Tetrahydrofuran
  • Cdimethicone is the dimethicone concentration in the GPC vial expressed in ppm ( ⁇ g dimethicone per gram of THF), mTHF the amount of THF, expressed in grams, used to re-solubilize the dimethicone in the evaporating dish and mhair, the amount of hair expressed in grams introduced in the polyethylene bottle.

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Abstract

L'invention porte sur un procédé qui permet de fabriquer une gomme de guar cationique en évitant sensiblement d'utiliser du bore, lequel procédé consiste à : faire réagir des particules de polysaccharide avec un agent de dérivatisation afin de produire des particules de polysaccharide dérivées; laver les particules de polysaccharide dérivées; et mettre en contact les particules de polysaccharide dérivées, avant ou après l'étape de lavage, avec un composé glyoxal afin de les réticuler. L'invention concerne également des procédés de fabrication de polysaccharides dérivés réticulés, lesquels procédés consistent à: (a) mettre en contact les particules d'un polysaccharide avec un composé titane dans un milieu aqueux à pH alcalin dans des conditions adéquates afin de réticuler les particules de manière intraparticulaire; (b) faire réagir les particules de polysaccharide, avant ou après l'étape de mise en contact de ces dernières avec le composé titane, avec un agent de dérivatisation dans des conditions adéquates afin de produire des particules de polysaccharide dérivées; (c) laver les particules dérivées et réticulées avec le titane; (d) mettre en contact les particules dérivées et réticulées avec le titane, pendant ou après l'étape de lavage de ces dernières, avec un milieu aqueux à pH acide dans des conditions adéquates afin de sensiblement déréticuler lesdites particules; et (e) mettre les particules déréticulées en contact, pendant ou après l'étape (d), avec un composé glyoxal dans des conditions appropriées afin de réticuler lesdites particules de manière intraparticulaire. La gomme de guar cationique selon l'invention est particulièrement utile dans les formulations de soins personnels et d'entretien de la maison, en particulier dans les formulations comprenant du silicone étant donné qu'elle améliore le dépôt du silicone.
PCT/US2009/000617 2008-01-31 2009-01-30 Polysaccharides réticulés et procédés de production WO2009099567A2 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
CA2713849A CA2713849C (fr) 2008-01-31 2009-01-30 Polysaccharides reticules et procedes de production
CN2009801038361A CN101932610B (zh) 2008-01-31 2009-01-30 交联多糖及其制备方法
BRPI0907029-0A BRPI0907029A2 (pt) 2008-01-31 2009-01-30 Polissacarídeos reticulados e método de produção dos mesmos
EP09708519.5A EP2245073A4 (fr) 2008-01-31 2009-01-30 Polysaccharides réticulés et procédés de production

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US2496508P 2008-01-31 2008-01-31
US61/024,965 2008-01-31
US13548108P 2008-07-21 2008-07-21
US61/135,481 2008-07-21

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WO2009099567A3 WO2009099567A3 (fr) 2009-12-30

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WO2011157505A1 (fr) 2010-06-18 2011-12-22 Rhodia Operations Protection de la coloration de fibres textiles par des polysaccharides cationiques.
WO2012042000A1 (fr) 2010-10-01 2012-04-05 Rhodia Operations Composition de nettoyage pour surface dure
EP3159384A1 (fr) 2015-10-20 2017-04-26 Rhodia Operations Revêtements primaires à base de polysaccharides cationiques destinés à des surfaces hydrophobes
US10273434B2 (en) 2010-06-18 2019-04-30 Rhodia Operations Protection of the color of textile fibers by means of cationic polysacchrides

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CA3044701A1 (fr) * 2016-11-23 2018-05-31 Integrity Bio-Chemicals Llc Compositions de polysaccharide reticule et melanges de beton contenant ces dernieres
FR3085164B1 (fr) * 2018-08-22 2021-02-26 Natvi Procede de lubrification
CN110845635B (zh) * 2019-11-29 2022-07-29 江苏哈齐诺生物环保科技有限公司 一种两性多糖吸水材料的制备方法

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WO2011157505A1 (fr) 2010-06-18 2011-12-22 Rhodia Operations Protection de la coloration de fibres textiles par des polysaccharides cationiques.
US10273434B2 (en) 2010-06-18 2019-04-30 Rhodia Operations Protection of the color of textile fibers by means of cationic polysacchrides
WO2012042000A1 (fr) 2010-10-01 2012-04-05 Rhodia Operations Composition de nettoyage pour surface dure
EP3159384A1 (fr) 2015-10-20 2017-04-26 Rhodia Operations Revêtements primaires à base de polysaccharides cationiques destinés à des surfaces hydrophobes
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US20090197829A1 (en) 2009-08-06
US8785622B2 (en) 2014-07-22
EP2245073A4 (fr) 2013-07-03
CN101932610A (zh) 2010-12-29
CN101932610B (zh) 2013-06-19
KR20100108575A (ko) 2010-10-07
WO2009099567A3 (fr) 2009-12-30
CA2713849C (fr) 2016-01-12
CA2713849A1 (fr) 2009-08-13
EP2245073A2 (fr) 2010-11-03
BRPI0907029A2 (pt) 2015-07-07

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